ELECTRO CHEMISTRY

Q1. What is meant by Limiting Molar Conductivity? (1)

Answer:
The molar conductivity of a solution at infinite dilution is called limiting molar conductivity and is
represented by the symbol Λm.

Q2. Express the relation among the cell constant , the resistance of the solution and the conductivity
of the solution. How is the conductivity of the solution related to its molar conductivity? (2)

Answer:
1/R×1/a = Conductance (C) × Cell constant
Molar conductance : (Λm) = K×1000/c.

Q3.Given that the standard electrode potentials (E°) of metals are :

K+/K = -2.93 V, Ag+/Ag = 0.80 V, Cu2+/Cu = 0.34 V,
Mg2+/Mg = -2.37 V, Cr3+/Cr = -0.74 V, Fe2+/Fe = -0.44 V.
Arrange these metals in increasing order of their reducing power. (All India 2010)
Answer:
Ag+/Ag < Cu2+/Cu < Fe2+/Fe < Cr3+/Cr < Mg2+/ Mg < K+/K
More negative the value of standard electrode potentials of metals is, more will be the
reducing power.
Q4. Two half cell reactions of an electrochemical cell are given below :
MnO–4(aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I), E° = + 1.51 V
Sn2+ (aq) → 4 Sn4+ (aq) + 2e–, E° = + 0.15 V
Construct the redox equation from the two half cell reactions and predict if this reaction favours
formation of reactants or product shown in the equation. (All India 2009)
Answer:
The reactions can be represented at anode and at cathode in the following ways :
At anode (oxidation) :
Sn2+ → = Sn4+ (aq) + 2e– ] × 5 E° = + 0.15 V
At cathode (reduction) :
MnO–4(aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I)] × 2 E° = + 1.51 V
The Net R × M = 2MnO–4(aq) + 16H+ + 5Sn2+ → 2Mn2+ + 5Sn4+ + 8H2O
Now E°cell = E°cathode – E°anode
= 1.51 – 0.15 = + 1.36 V
∴ Positive value of E°cell favours formation of product.
Q5. Determine the values of equilibrium constant (Kc) and ΔG° for the following reaction :
Ni(s) + 2Ag+ (aq) → Ni2+ (aq) + 2Ag(s),
E° = 1.05 V
(1F = 96500 C mol-1) (Delhi 2011)
Answer:
According to the formula
ΔG° = -nFE° = – 2 × 96500 ×1.05
or ΔG° = -202650 J mol-1 = -202.65 KJ mol-1
Now ΔG° ⇒ -202650 J Mol-1
R = 8.314 J/Mol/K, T = 298 K
Q6.Express the relation among cell constant, resistance of the solution in the cell and conductivity of
the solution. How is molar conductivity of a solution related to its conductivity? (All India 2012)
Answer:
GG* = K
where Q is conductance;
G * is cell constant;
K is conductivity
G* × 1/R = K ⇒ G* = RK
∴ Λm = K×1000/C S cm2 mol-1
Q7.The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm2 mol-1.
Calculate the conductivity of this solution. (All India 2012)
Answer:
C = 1.5 M, Λm = 138.9 S cm2 mol-1
Λm = K×1000/c
∴K = Λm×C1000=138.9×1.5/1000 = 0.20835 S cm-1

Q8.The conductivity of 0.20 M solution of KCl at 298 K is 0.025 S cm-1. Calculate its molar
conductivity. (Delhi 2013)
Answer:
Molar conductivity Λm = 1000×κM
Given : K = 0.025 S cm-1, M = 0.20 M
Hence, Λm = 0.025×10000.20 ∴ Λm = 125 S cm2 mol-1
Q9.The standard electrode potential (E°) for Daniel cell is +1.1 V. Calculate the ΔG° for the
reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
(1 F = 96500 C mol-1). (All India 2013)
Answer:
We know, ΔG° = -nF E°cell
Given : E°cell = 1.1 volt
∴ ΔG° = -2 × 96500 C mol-1 × 1.1 volt
= -212300 CV mol-1
= -212300 J mol-1 = -212.3 KJ mol-1

Q10. Calculate the degree of dissociation (a) of acetic acid if its molar conductivity (Λ m) is 39.05 S
cm2 mol-1.
Given: λ°(H+) = 349.6 S cm2 mol-1 and λ°(CH3COO–) = 40.9 S cm2 mol-1 (Delhi 2017)
Answer:
Λ°m(HAC) = λ°H + λ°AC
+ –

= λ°CH COOH = λ°H + λ°CH COO

3
+
3
–

= 349.6 S cm2 mol-1 + 40.9 S cm2 mol-1

= 390.5 S cm2 mol-1

Q11.The electrical resistance of a column of 0.05 M NaOH solution of diameter 1 cm and length 50
cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.(All India 2012)
Answer:
A = πr2 = 3.14 × (0.5)2 = 0.785 cm2, l = 50 cm

Q12. A voltaic cell is set up at 25°C with the following half cells :
Al/Al3+ (0.001 M) and Ni/Ni2+ (0.50 M)
Write an equation for the reaction that occurs when the cell generates an electric current and
determine the cell potential.
E0Ni2+/Ni=−0.25V and E0Al3+/Al=−1.66V
(Log 8 × 10-6 = -0.54) (All India 2012)
Answer:
Half cell reactions and overall cell reaction are
Q13. When a certain conductance cell was filled with 0.1 M KCl, it has a resistance of 85 ohms at
25°C. When the same cell was filled with an aqueous solution of 0.052 M unknown electrolyte, the
resistance was 96 ohms. Calculate the molar conductance of the electrolyte at this concentration.
[Specific conductance of 0.1 M KCl = 1.29 × 10-2 ohm-1 cm-1] (Comptt. All India 2012)
Answer:
Cell contant = Conductivity × Resistance
G* = K × R
= 1.29 × 10-2Ω-1 × 85
= 109.65 × 10-2Ω-1
= 1.0965 cm-1

Q14. The cell in which the following reaction occurs :

2Fe3+ (aq) + 2I– (aq) → 2Fe2+ (aq) + I2 (s) has E0cell = 0.236V at 298K. Calculate the standard
Gibbs energy and the equilibrium constant of the cell reaction.
(Antilog of 6.5 = 3.162 × 106; of 8.0 = 10 × 108; of 8.5 = 3.162 × 108) (Comptt. All India
2012)
Answer:
log KC = nE0 cell 0.0591=2×0.2360.0591 = 8
KC = antilog 8 = 1 × 108
ΔG° = -nFE0cell = -2 × 96500 × 0.236
= -45548 J/mol-1
= -45.548 kJ/mol-1

Q15.Calculate the emf of the following cell at 298 K: Fe(s) | Fe2+ (0.001 M) || H+ (1M) | H2(g)
(1 bar), Pt(s) (Given E°cell = +0.44V) (Delhi 2013)
Answer:
As Fe + 2H+ → Fe2+ + H2 (n = 2)
According to Nernst equation

Q16.Calculate the emf of the following cell at 25°C : Ag(s) | Ag+ (10-3 M) || Cu2+ (10-1 M) |
Cu(s) Given E0cell = +0.46 V and log 10n = n. (All India 2013)
Answer:
Given: Cell notation is incorrect. Correct cell formula is
Cu2+ (10-1 m) | Cu(5) || Ag+ (10-3 M) | Ag(s)
According to Nernst equation

∴Ecell = 0.46 V – 0.14775 = 031 V

Q17. Calculate emf of the following cell at 25°C :

Fe | Fe2+ (0.001 M) || H+ (0.01 M) | H2(g) (1 bar) | Pt(s)
E0(Fe2+ | Fe) = -0.44 V E0(H+ | H2) = 0.00V (Delhi 2015)
Answer:
Fe | Fe2+ (0.001 M) || H+ (0.01 M) | H2(g) (1 bar) | Pt(s)

= 0.4105 Volts

Q18. Conductivity of 2.5 × 10-4 M methanoic acid is 5.25 × 10-5 S cm-1. Calculate its molar
conductivity and degree of dissociation.
Given : λ0(H+) = 349.5 Scm2 mol-1
and λ0(HCOO–) = 50.5 Scm2 mol-1. (All India 2015)
Answer:
Concentration is 2.5 x 10-4 M
K = 5.25 × 10-5 Scm-1.
Λcm=K×1000 Concentration

Q19. Calculate e.m.f. of the following cell at 298 K: 2Cr(s) + 3Fe2+ (0.1 M) → 2Cr3+ (0.01
M) + 3 Fe(s)
Given: E0(Cr3+| Cr) = -0.74 V E0(Fe2+ | Fe) = -0.44 V (Delhi 2016)
Answer:
Cell reaction: 2Cr(s) + 3Fe2+ (0.1 M) → 2Cr3+ (0.01 M) + 3Fe(s)
Given: E0(Cr3+/Cr) = -0.74
E0(Fe2+/Fe) = -0.44 V

Q20. (a) The cell in which the following reaction occurs:

2Fe3+ (aq) + 2I–(aq) → 2Fe2+ (aq) + I2(s)
has Eo Cell = 0.236 V at 298 K. Calculate the standard Gibbs energy of the cell reaction.
(Given: 1F = 96,500 C mol-1)
(b) How many electrons flow through a metallic wire if a current of 0.5 A is passed for 2
hours? (Given: 1F = 96,500 C mol-1) (All India 2017)
Answer:
(a) 2Fe3+ (aq) + 2I– (aq) → 2Fe2+ (aq) + I2 (s)
For the given reaction, n = 2, E° = 0.236 V
Using formula
ΔG° = -nF E°cell
= -2 × 96,500 C mol-1 × 0.236 V
∴ ΔG° =-45.55 kj mol-1
(b) Given:
I = 0.5 A
t = 2 hrs. = 2 × 60 ×60 s = 7,200 s
Q = I × t = 0.5 × 7200 = 3,600 C
96,500 C electricity flows to produce
= 6.022 × 1023 electrons
∴ 1 C electricity flows to produce

Q21. Why an electrochemical cell stop working after some time? The reduction potential of
an electrode depends upon the concentration of solution with which it is in contact. (All India
2017)
Answer:
As the cell works, the concentration of reactants decrease. Then according to Le chatelier’s
pri¬nciple it will shift the equilibrium in backward direction. On the other hand if the
concentration is more on the reactant side then it will shift the equilibrium in forward
direction. When cell works concentration in anodic compartment in cathodic compartment
decreases and hence E° cathode will decrease. Now EMF of cell is
E0cell = E0cathode – E0anode
A decrease in E°cathode and a corresponding increase in E°anode will mean that EMF of the
cell will decrease and will ultimately become zero i.e., cell slops working after some time.
Q22.Calculate ΔrG° and log Kc for the following reaction at 298 K.
2Cr(s)+3Cd2+(aq)⟶2Cr3+raq+3Cd(s)
[Given : E0Cell = +0.34 V, IF = 96500 C mol-1] (Comptt. All India 2017)
Answer:
Q23.Calculate ΔrG° and log K. for the following reaction at 298 K. (Comptt. All India 2017)

Answer:

Q24.(a) Define molar conductivity of a substance and describe how for weak and strong
electrolytes, molar conductivity changes with concentration of solute. How is such change
explained?
(b) A voltaic cell is set up at 25°C with the following half cells :
Ag+ (0.001 M) | Ag and Cu2+ (0.10 M) | Cu What would be the voltage of this cell? (E0cell =
0.46 V) (Delhi 2009)
Answer:
(a) Molar conductivity: Molar conductivity of a solution at a given concentration is tire
conductance of the volume ‘V’ of a solution containing one mole of electrolyte kept between
two electrodes with area of cross section ‘A’ and distance of unit length. It is represented by
Λm (lamda).
Λm = KAl ∴ l = 1 and A = V
∴ Λm= KV Unit = S cm2 mol-1
Effect of change of concentrations on molar conductivity. In case of strong electrolytes there
is a small increase in conductance with dilution because a strong electrolyte is completely
dissociated in solution and the number of ions remains constant. Moreover there will be
greater inter-ionic attractions at higher concentrations which retards the motion of ions and
conductance decreases. In case of weak electrolytes there is increase in conductance with
decrease in concentration due to the increase in the number of ions in the solution.
The graph between Λm and concentration also rectifies the above statement.

(b) The reaction takes place in cell as

= 0.46 – 0.0592 × 5
= 0.46 – 0.1475 = 0.3125
Q25.(a) State the relationship amongst cell constant of a cell, resistance of the solution in the
cell and conductivity of the solution. How is molar conductivity of a solute related to
conductivity of its solution?
(b) A voltaic cell is set up at 25°C with the following half-cells :
Al | Al3+ (0.001 M) and Ni | Ni2+ (0.50 M)
Calculate the cell voltage
E0Ni2+/Ni=−0.25V,E0Ni2+/Ni=−1.66V
(Delhi 2009)
Answer:
(a) The relationship between the cell constant of a cell (G*), resistance of the solution in the
cell (R) and conductivity (K) is given by
K = Cell constant R=G⋆R
The relationship between molar conductivity (Λm) and conductivity of the solution (K) is
given by
Λm = KC

(b) The cell may be represented as

Al | Al3+ || Ni2+| Ni
E0cell = E0R – E0L
E0cell = (-0-25) – (-1.66)
∴ E0 = -0.25 + 1.66 = 1.41 V

Q27.(a) State Kohlrausch law of independent migration of ions. Write an expression for the
molar conductivity of acetic acid at infinite dilution according to Kohlrausch law.
(b) Calculate Λ°m for acetic acid.
Given that Λ°m (HCl) = 426 S cm2 mol-1
Λ°m (NaCl) = 126 S cm2 mol-1
Λ°m (CH3COONa) = 91 S cm2 mol-1 (Delhi 2010)
Answer:
(a) Kohlrausch law of independent migration of ions : The limiting molar conductivity of an
electrolyte (i.e. molar conductivity at infinite dilution) is the sum of the limiting ionic
conductivities of the cation and the anion each multiplied with the number of ions present in
one formula unit of the electrolyte

Q28.(a) Predict the products of electrolysis in each of the following:

(i) An aqueous solution of AgNO3 with platinum electrodes.
(ii) An aqueous solution of H2SO4 with platinum electrodes.
(b) Estimate the minimum potential difference needed to reduce Al2O3 at 500°C. The Gibbs
energy change for the decomposition reaction 23 Al2O3 → 43 Al + O2 is 960 kJ
(F = 96500 C mol-1) (Comptt. Delhi 2014)
Answer:

Q29.(a) Define the term degree of dissociation. Write an expression that relates the molar
conductivity of a weak electrolyte to its degree of dissociation.
(b) For the cell reaction
Ni(s) | Ni2+(aq) || Ag+(aq) | Ag(s)
Calculate the equilibrium constant at 25 °C. How much maximum work would be obtained
by operation of this cell?
EoNi2/Ni = 0.25 V and EoAg+/Ag = 0.80 V (Comptt. Delhi 2014)
Answer:
(a) Degree of dissociation: It is the measure of the extent to which an electrolyte gets
dissociated into its constitutent ions.
Thus higher the degree of dissociation, higher will be its molar conductance. Mathematically
it can be expressed as :
Maximum work = 106.150 KJ mol-1

Q30.Calculate ΔrG° and e.m.f. (E) that can be obtained from the following cell under the
standard conditions at 25°C :
Zn (s) | Zn2+ (aq) || Sn2+ (aq) | Sn (s)
Answer:

Q31.(a) Calculate E0cell for the following reaction at 298 K:

2Al(s) + 3Cu2+ (0.01M) → 2Al2+ (0.01M) + 3Cu(s)
Given: Ecell = 1.98 V
(b) Using the E0 values of A and B, predict which is better for coating the surface of iron
[E0(Fe2+/Fe) = -0.44 V] to prevent corrosion and why?
Given: E0(A2+/A) = -2.37 V; E0(B2+/B) = -0.14 V (All India 2016)
Answer:
(a) For the reaction
2Al(s) + 3Cu2+ (0.01M) → 2Al3+ (0.01M) + 3Cu(s)
Given: Ecell = 1.98 V E0cell = ?
Using Nernst equation

(b) Element A will be better for coating the surface of iron than element B because its E°
value is more negative.
Q32.(a) When a bright silver object is placed in the solution of gold chloride, it acquires a
golden tinge but nothing happens when it is placed in a solution of copper chloride. Explain
this behaviour of silver.
[Given : E0Cu2+/Cu =+0.34V,E0Ag+/Ag =+0.80V, E0Au3+/Au = +1.40V]
(b) Consider the figure given and answer the following questions :
(i) What is the direction of flow of electrons?
(ii) Which is anode and which is cathode?
(iii) What will happen if the salt bridge is removed?

(iv) How will concentration of Zn2+ and Ag+ ions be affected when the cell functions?
(v) How will concentration of these ions be affected when the cell becomes dead? (Comptt.
Delhi 2017)
Answer:
(a) The standard electrode potential, E° for silver is 0.80 V and that of gold is 1.5 V, hence
silver can displace gold from its solution. The replaced gold is deposited on silver object due
to which golden tinge is obtained. On the other hand E° for Cu is 0.34 V which is lower than
that of silver, thus silver cannot replace copper from its solution.

(b)

(i) Electrons flow from anode (Zinc plate) to cathode (Silver plate).
(ii) Zinc plate where oxidation occurs acts as anode and silver plate where reduction occurs
acts as cathode.
(iii) If the salt bridge is removed then electrons from zinc electrode will flow to the silver
electrode where they will neutralize some of Ag+ ions and the SO2−4 ions will be left and the
solution will acquire a negative charge. Secondly the Zn2+ ions from zinc plate will enter into
ZnSO4 solution producing positive charge. Thus due to accumulation of charges in two
solutions, further flow of electrons will stop and hence the current stops flowing and the cell
will stop functioning.
(iv) As silver from silver sulphate solution is deposited on the silver electrode and sulphate
ions migrate to the other side, the concentration of AgSO4 solution decreases and of
ZnSO4 solution increases as the cell operates.
(v) When the cell becomes dead, the concentration of these ions become equal due to
attainment of equilibrium and zero EMF.
Q33. (a) What is limiting molar conductivity? Why there is steep rise in the molar
conductivity of weak electrolyte on dilution?
(b) Calculate the emf of the following cell at 298 K :
Mg (s) | Mg2+ (0.1 M) || Cu2+ (1.0 × 10-3M) | Cu (s)
[Given = E0 Cell = 2.71 V]. (Comptt. Delhi 2017)
Answer:
(a) The molar conductivity of a solution at infinite dilution is called limiting molar
conductivity and is represented by the
symbol Λ∘m
There is steep rise in the molar conductivity of weak electrolyte on dilution because as the
concentration of the weak electrolyte is reduced, more of it ionizes and thus increase in the
number of ions in the solution.